CN104326637B - A kind of method for sludge treatment - Google Patents
A kind of method for sludge treatment Download PDFInfo
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- CN104326637B CN104326637B CN201410563428.7A CN201410563428A CN104326637B CN 104326637 B CN104326637 B CN 104326637B CN 201410563428 A CN201410563428 A CN 201410563428A CN 104326637 B CN104326637 B CN 104326637B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
Abstract
Embodiments provide a kind of method for sludge treatment, belong to field of sludge treatment, it is possible to process mixing sludge rationally and effectively, solve city environmental pollution problem.Described method for sludge treatment, including: municipal sludge and steel mill's mud are mixed, obtains mixing sludge；After described mixing sludge is ground, sieves, it is carried out heat exchange and sends in reactor；In described reactor, described mixing sludge in the supercritical state with oxidant generation oxidation reaction, reaction of formation product；Described reaction product carries out high-pressure gas-liquid separation after cooling, obtains power tail gas, CO2Gas and the pulp water rich in metal-oxide.The present invention can be used in the Combined Treatment of municipal sludge and steel mill's mud.
Description
Technical field
The present invention relates to field of sludge treatment, particularly relate to a kind of method for sludge treatment.
Background technology
In recent years, along with economic fast development has driven the quickening of urbanization process, municipal administration is dirty
The treating capacity of water is increasing so that the mud produced after flocculating sedimentation in sewage disposal process
Quantity increases therewith.It addition, along with the development of steel and iron industry, substantial amounts of steel mill mud is the most therewith
Produce.Municipal sludge and steel mill's mud constitute the main source of mixing sludge, wherein, steel mill
Rich in abundant transition metal in mud, such as Fe, Mn, Ni, Cr, Mo, V, Ti,
Zn, Cu, As etc., be composition common in steel mill's mud, and municipal sludge has higher heat
Value.But owing to the two all containing substantial amounts of water so that it is be difficult to be recycled economically.
At present, mostly use traditional sludge incineration method that mixing sludge is processed, i.e. exist
Mud is collected and adds substantial amounts of combustible after dehydrate process and ignite, put in incinerator
Burn.Owing to the moisture of mud is big, this burning mode can make fire box temperature low,
Burn insufficient, and callable heat is few, so generally coal, oil also can be blended wherein
Jiao etc. has the higher fuel of calorific value, but finally also has insufficient the consolidating of more burning after burning
Body residue, and have containing a large amount of oxysulfides, nitrogen oxides and two English classes in tail gas
Poison harmful gas, time serious, steel mill's mud also can produce plurality of heavy metal oxide through burning
The dust granules such as PM2.5, PM10, metallic element therein particularly heavy metal element, such as
Ni, Cr, Cu, Zn, As etc. can form small of metal-oxide during high temperature incineration
Grain, the collection of this molecule and trap extremely difficult, easily enter air with tail gas, right
Air, soil, subsoil water and health all produce harmful effect.
Preferably can be relevant to steel mill mud Combined Treatment to municipal sludge owing to there is presently no
Technology, so processing mixing sludge the most rationally and effectively, both can make full use of mud
The catalysis activity of middle metal ion, the pollution problem simultaneously solving urban environment is art technology
The important topic that personnel are faced.
Summary of the invention
Embodiments provide a kind of method for sludge treatment, it is possible to process mixed rationally and effectively
Close mud, solve city environmental pollution problem.
For reaching above-mentioned purpose, embodiments of the invention adopt the following technical scheme that
A kind of method for sludge treatment, including:
Municipal sludge and steel mill's mud are mixed, obtains mixing sludge；
After described mixing sludge is ground, sieves, it is carried out heat exchange and sends into reactor
In；
In described reactor, described mixing sludge in the supercritical state with oxidant generation oxygen
Change reaction, reaction of formation product；
Described reaction product carries out high-pressure gas-liquid separation after cooling, obtains power tail gas, CO2
Gas and the pulp water rich in metal-oxide.
Optionally, described steel mill mud account for described mixing sludge mass percent 5～30%.
Optionally, described steel mill mud include selected from Fe, Mn, Ni, Cr, Mo, V, Ti,
The transition metal of Zn, Cu, to account for the mass percentage of described steel mill mud, Fe is 5～50%,
Mn is 0.1～10%, and Ni is 0.1～20%, and Cr is 0.1～15%, and Mo is 0.05～5%, V
Being 0.01～3%, Ti is 0.01～2%, and Zn is 0.02～5%, and Cu is 0.1～10%.
Optionally, described reaction product carries out high-pressure gas-liquid separation after cooling, obtains power
Tail gas, CO2Gas and the pulp water rich in metal-oxide include:
In the first high-pressure gas-liquid separator, described reaction product is carried out one-level high-pressure gas-liquid to divide
From, to generate power tail gas and intermediate reaction product；
In the second high-pressure gas-liquid separator, described intermediate reaction product is carried out two grades of high pressure gas
Liquid separates, to generate CO2Gas and the pulp water rich in metal-oxide.
Optionally, any one in air, oxygen and hydrogen peroxide of described oxidant.
Optionally, the operation pressure of described oxidation reaction is 22～30MPa, and temperature is
380～900 DEG C.
Further, the operation pressure of described oxidation reaction is 22～26MPa, and temperature is
420～650 DEG C.
Optionally, during the stop in described first high-pressure gas-liquid separator of the described reaction product
Between be 5～60min.
Further, described reaction product stop in described first high-pressure gas-liquid separator
Time is 15～40min.
Optionally, the inlet temperature of described first high-pressure gas-liquid separator, below 31 DEG C, exports
Pressure is at more than 7.38MPa.
Optionally, before or after described mixing sludge being ground and sieves, to described mixing
Mud adds complexing agent, to improve the concentration of described mixing sludge.
Embodiments providing a kind of method for sludge treatment, this method utilizes water at supercritical
The special nature being had under state, makes mixing sludge and oxidant send out rapidly in supercritical water
Raw reaction thoroughly decomposes mixing sludge, to generate CO2Gas and the slag rich in metal-oxide
Water.In the method, not only can be to CO2Realize recycling, also can make in organic matter
N, S, P element have obtained effectively converting, it is achieved that harmless treatment.Simultaneously as steel
Containing transition metal in large quantities in factory's mud, it is played under supercritical water oxidation effect
The effect of catalysis oxidation, also achieves the enrichment of transition metal, is particularly advantageous in containing weight
The later stage harmless treatment of metallic element mud, reduces the negative effect in terms of environment.
Accompanying drawing explanation
The flow chart of the method for sludge treatment that Fig. 1 provides for the embodiment of the present invention；
The sludge treatment equipment that utilizes that Fig. 2 provides for the embodiment of the present invention carries out the work of Treatment of Sludge
Process flow figure；
Legend:
A1 be oxidant, a2 be raw water, a3 be compounding mud, b1 be tail gas 1, b2 be tail
Gas 2, b3 be pulp water, b4 be biosolid waste；
1 be transmission system, 2 be blending tank, 3 for pump 1,4 be grinder, 5 be screening machine,
6 be surge tank, 7 for pump 2,8 be head tank, 9 be high mudjack, 10 be heat-exchange system,
11 it is response system, 12 is blood pressure lowering system for high pressure knockout drum 1,13 for high pressure knockout drum 2,14
System, 15 decompressors, 16 be air relief valve 1,17 for air relief valve 2,18 be booster pump or compressor,
19 is cooler.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, to the technical side in the embodiment of the present invention
Case is clearly and completely described, it is clear that described embodiment is only the present invention one
Divide embodiment rather than whole embodiments.Based on the embodiment in the present invention, this area is general
The every other embodiment that logical technical staff is obtained under not making creative work premise,
Broadly fall into the scope of protection of the invention.
The method for sludge treatment provided the embodiment of the present invention below in conjunction with the accompanying drawings is retouched in detail
State.
The flow chart of the method for sludge treatment that Fig. 1 provides for the embodiment of the present invention.As it is shown in figure 1,
Embodiments provide a kind of method for sludge treatment, including:
S1: municipal sludge and steel mill's mud are mixed, obtains mixing sludge；
In this step, municipal sludge and steel mill's mud are mixed, obtain mixing sludge,
To realize the coupling processing to described mixing sludge.Wherein, municipal sludge from municipal sewage,
Steel mill's mud is different with equipment due to technique, may be from cold rolling hot rolling steel mill, blast furnace, oxygen
Top blast stove (top blast stove, converter, bottom convertor), pickling and electroplating activity, heat treatment factory, new
Formula open hearth etc..For municipal sludge, steel mill's mud is mainly by water with from converter waste gas
Ferric oxide particles composition under washing, and containing abundant transition metal.It is understood that
Typically require when described steel mill mud is mixed with municipal sludge and mix homogeneously, and mix tune
The method of joint can use the conventional method that those skilled in the art are obtained, and the embodiment of the present invention is not
It is specifically limited.
S2: after described mixing sludge is ground, is sieved, carries out heat exchange to it and sends into anti-
Answer in device.
In this step, mixing sludge need to be ground, sieve, this is because sewage disposal
The mud of rear generation often carries bigger granule secretly, if be sent directly in process unit, easy
Causing the blocking of pipeline, being normally carried out of impact reaction, therefore, before sending into process unit
Need to carry out pre-treatment, mud pre-treatment comprises mud dilution, grinding, filter process, and it is main
Process means are to grind and screening filtration.Such as, can reasonably control the rotating speed of grinder and grind
Distance between grinding machine rotor and stator, with the bulky grain in ground and mixed mud effectively, from
And ensure that mixing sludge can be normally carried out in next reaction of entrance.In mud to be mixed big
Before grain sends into reactor after effectively being ground, also needing it is carried out heat exchange, this is primarily due to
Mainly happens is that in reactor that supercritical oxidation reacts, temperature is higher, in order to promote supercritical
The generation of reaction, first can carry out heat exchange to the mixing sludge after grinding screening.May be appreciated
It is that the temperature reached after heat exchange is about the temperature that supercritical reaction occurs.
S3: in described reactor, described mixing sludge is sent out with oxidant in the supercritical state
Raw oxidation reaction, reaction of formation product.
Supercritical water refer to temperature and pressure be above its critical point (T=374.15 DEG C,
The water of special state P=22.12MPa).Supercritical water has the character of liquid and vaporous water concurrently,
Hydrogen bond the most a small amount of under this state exists, and dielectric constant is similar to organic solvent, has high
Diffusion coefficient and low viscosity.At high enough pressure, can not only make in mixing sludge
Organic substance and oxygen dissolve each other with supercritical water in any proportion, additionally it is possible to make inorganic matter particularly salt
Class is separated from supercritical water.
In this step, utilize the special nature that water is had in the supercritical state, make mixing
Mud and oxidant react rapidly reaction of formation product in supercritical water, with thoroughly point
Solve mixing sludge.Wherein, the reaction of main generation is:
C+H2O→CO+H2
C+2H2O→CO2+2H2
CO+H2O→CO2+H2
CO+3H2→CH4+H2O
CO2+4H2→CH4+2H2O
C+O2→CO2
2CO+O2→2CO2
CH4+2O2→CO2+2H2O
2H2+O2→2H2O
Described mixing sludge and the most reacted reaction product of oxidant are main
Including CO, N2、O2、CH4With a small amount of CO2Gas, and reacted mixing sludge
Pulp water.Due to CO, N2、O2、CH4With a small amount of CO2Gas can promote after isolation
Extender acting generating, so by CO, N in the present embodiment2、O2、CH4With a small amount of CO2
It is referred to as power tail gas.
S4: described reaction product carries out high-pressure gas-liquid separation after cooling, obtain power tail gas,
CO2Gas and the pulp water rich in metal-oxide.
In this step, the reaction product that supercritical reaction generates need to be re-fed into after cooling
Carrying out high-pressure gas-liquid separation in high-pressure gas-liquid separator, this occurs in being primarily due to reactor
Being supercritical reaction, reaction temperature is higher, and to CO in high-pressure gas-liquid separator2Gas and
Other power tail gas then needs according to CO when separating2Critical pressure and the critical temperature of gas are entered
Row operation, so need to cool down reaction product, chilling temperature is about to CO2Facing of gas
Below boundary's temperature, to ensure CO2Gas is substantially effectively separated with power tail gas, permissible
Being understood by, critical pressure specifically can be according to CO2Percentage composition in gas component determines
CO2Dividing potential drop when liquefaction.
It should be noted that in embodiments of the present invention, described mixing sludge includes municipal sludge
With steel mill's mud.It is understood that owing to the place of steel mill's mud output has a lot, such as
Including cold rolling hot rolling steel mill, blast furnace, oxygen top blown stove (top blast stove, converter, bottom convertor),
Pickling and electroplating activity, heat treatment factory etc., so not doing concrete limit to the concrete source of mud
Fixed, as long as mud, the most only process municipal sludge or only process steel mill's mud, no matter also
It is Combined Treatment municipal sludge and steel mill's mud, all may utilize Treatment of Sludge provided by the present invention
Method processes.
Embodiments providing a kind of method for sludge treatment, this method utilizes water at supercritical
The special nature being had under state, makes mixing sludge and oxidant send out rapidly in supercritical water
Raw reaction thoroughly decomposes mixing sludge, to generate CO2Deng gas with rich in metal-oxide
Pulp water.In the method, not only can be to CO2Realize recycling, also can make in organic matter
N, S, P element obtained effectively converting, it is achieved that harmless treatment.Simultaneously as
Containing transition metal in large quantities in steel mill's mud, it is risen under supercritical water oxidation effect
To catalysis oxidation effect, also achieve the enrichment of transition metal, be particularly advantageous in containing
The later stage harmless treatment of heavy metal element mud, reduces the negative effect in terms of environment.
In one embodiment of this invention, described steel mill mud accounts for the quality hundred of described mixing sludge
The 5～30% of mark.In order to reasonably utilize and process steel mill's mud and municipal sludge, in this reality
Execute in example, scientifically control the adding proportion of steel mill's mud and municipal sludge.This is primarily due to,
If ratio is too low, the metal element content playing catalytic action in the most described steel mill mud is not enough, difficult
To play catalytic action, or do not reach preferable catalytic condition；If ratio is too high, then can affect
Mixed sludge calorific value, certainly, although can by add other auxiliary fuel such as methanol,
The calorific value that ethanol, used oil etc. adjust mixing sludge is anti-with the chemistry ensureing normal self-heating
Answer process, but if able to control steel mill's mud and the ratio of municipal sludge with more reasonable manner
Example, then can need not be added to other fuel, thus control operating cost.May be appreciated
Be, described steel mill mud accounts for the 10% of mass percent of described mixing sludge, 15%, 20%,
25% etc..
In one embodiment of this invention, described steel mill mud include selected from Fe, Mn, Ni, Cr,
The transition metal of Mo, V, Ti, Zn, Cu, to account for the mass percentage of described steel mill mud,
Fe is 5～50%, and Mn is 0.1～10%, and Ni is 0.1～20%, and Cr is 0.1～15%, and Mo is
0.05～5%, V are 0.01～3%, and Ti is 0.01～2%, and Zn is 0.02～5%, and Cu is 0.1～10%.
Rich in substantial amounts of transition metal in described steel mill mud, these transition metal can be at supercritical water oxygen
Play the effect of catalysis oxidation under change effect, thus can accelerate the response time of W-response, fall
Low reaction activation energy, technological operation optimization condition.By the ratio in the transition metal in steel mill's mud
Example regulation and control in above-mentioned proportion, can make transition metal in steel mill's mud more manage reaching
While the catalytic condition thought, do not affect the calorific value of described mixing sludge, thus dirty to steel mill
Mud and municipal sludge ensure during realizing coupling processing that the chemical reaction of normal self-heating is sent out
Raw.
In one embodiment of this invention, described reaction product carries out high-pressure gas-liquid after cooling
Separate, obtain power tail gas, CO2Gas and the pulp water rich in metal-oxide include: first
High-pressure gas-liquid separator carries out one-level high-pressure gas-liquid separation to described reaction product, to generate
Power tail gas and intermediate reaction product；In the second high-pressure gas-liquid separator anti-to described centre
Answer product to carry out two grades of high-pressure gas-liquids to separate, to generate CO2Gas and rich in metal-oxide
Pulp water.
In the present embodiment, first need reaction product is cooled down, be sent to the most again
First high-pressure gas-liquid separator separates.In the preferred embodiment of the present invention, described
The inlet temperature of one high-pressure gas-liquid separator controls below 31 DEG C, and outlet pressure controls
More than 7.38MPa.So can ensure CO2Gas with reaction after remaining pulp water still with liquid
State exists, thus realizes separating with power tail gas.
In the present embodiment, the CO after separation2After gas and reaction, remaining pulp water is admitted to the
Two high-pressure gas-liquid separators separate.It should be noted that the second high-pressure gas-liquid now divides
Inlet pressure from device still needs to be maintained at more than 7.38MPa, to keep CO2After gas and reaction
Remaining pulp water can together enter in the second high-pressure gas-liquid separator and be separated.High second
Calm the anger in liquid/gas separator, CO2Gas is separated through decompression by depressurized system, due to now
Gas is only left CO2Gas, so available highly purified CO after Fen Liing2Gas.Can manage
Solving, depressurized system can use air relief valve to control pressure, it is possible to use capillary tube blood pressure lowering fills
Put, to reduce pressure to normal pressure.Treat CO2After gas separates, in the second high-pressure gas-liquid separator
Pulp water also through decompression separated.It should be noted that pulp water now can be divided further
From for solid slag and pulp water, wherein, solid slag can be used for reclaiming flocculant and metal-oxide,
In the most recyclable preparation reusing mixing mud as raw water of pulp water.It is appreciated that
, about the subsequent treatment of pulp water, those skilled in the art can locate according to actual needs
Reason.
In one embodiment of this invention, described oxidant is in air, oxygen and hydrogen peroxide
Any one.Above-mentioned gas is selected can preferably to meet oxygen under super critical condition as oxidant
Change the generation of reaction, additionally can avoid introducing other impurity in reaction.
In one embodiment of this invention, the operation pressure of described oxidation reaction is 22～30MPa,
Temperature is 380～900 DEG C.Described operation pressure can be 24,26,28MPa, described temperature is
400℃、450℃、500℃、550℃、600℃、650℃、700℃、750℃、800℃、
850℃.The operation pressure of oxidation reaction, temperature are selected within the above range, can preferably protect
The generation of card oxidation reaction.In the preferred embodiment of the present invention, the behaviour of described oxidation reaction
Being 22～26MPa as pressure, temperature is 420～650 DEG C.
In one embodiment of this invention, described reaction product divides at described first high-pressure gas-liquid
The time of staying in device is 5～60min.The described time of staying can be 10,20,30,40,
50min.Mixing sludge and oxidant are reacted a period of time in the reactor, it is ensured that mixing dirt
Mud reacts with the abundant of oxidant.In the preferred embodiment of the present invention, described reaction generates
The thing time of staying in described first high-pressure gas-liquid separator is 15～40min.
In one embodiment of this invention, described mixing sludge is ground and sieve front or
After, in described mixing sludge, add complexing agent, to improve the concentration of described mixing sludge.To
Described mixing sludge adds complexing agent can grind and before screening, it is possible to grinding and sieve
Carrying out after/, its object is to improve the concentration of described mixing sludge, complexing agent such as can make
With lignosulfonates and the mixture of humate.It is understood that the present embodiment is not
Selection to complexing agent is defined, as long as the concentration of described mixing sludge can reasonably be improved,
Those skilled in the art all can use.
Illustrate below in conjunction with accompanying drawing 2 that to utilize sludge treatment equipment to carry out provided herein
The technological process of Treatment of Sludge.
As in figure 2 it is shown, raw material a2 and a3 is transported to blending tank (2), warp according to a certain percentage
After stirring, pump 1 (3) it is delivered to grinder and grinds (4), the sludge slurry warp after grinding
After screening machine (5) filters, filter screen upper strata is waste material (b4), and lower floor's mud enters surge tank (6),
And it is delivered to head tank (8) by pump 2 (7).Raw sludge is delivered to by high mudjack (9)
Heat-exchange system (10), enters response system (11) after heat exchange, and from booster pump (18)
Oxidant (a1) reaction, reaction product enters cooler (19) after heat-exchange system (10),
Subsequently into the first high-pressure gas-liquid separator (12), keeping certain time of staying, first is high
Liquid/gas separator (12) upper end outlet product of calming the anger can promote decompressor (15) acting generating, warp
Tail gas b1 (CO, N is obtained after air relief valve 1 (16)2、O2、CH4With a small amount of CO2).The
One high-pressure gas-liquid separator (12) lower end outlets products enters the second high-pressure gas-liquid separator (13),
Upper end product obtains tail gas b2 (CO after air relief valve 2 (17)2Gas), lower end product enters
Depressurizing system (14), decompression afterproduct is b3 (rich in the pulp water of metal-oxide), and b3 divides
The water separated out can reuse be used for reclaiming flocculation as raw water (a2), the isolated solid slag of b3
Agent and metal-oxide.
In order to a kind of method for sludge treatment that the present invention provides more preferably is described, below to be embodied as
Example is described in detail.Wherein, table 1 lists the fundamental property of municipal sludge, and table 2 is listed
The fundamental property of steel mill's mud, table 3 lists the percentage composition of steel mill's metal in sludge element.
The fundamental property of table 1 municipal sludge
The fundamental property of table 2 steel mill mud
Remarks: ar is As-received result, and d is for being dried base junction fruit.
Table 3 metallic element percentage composition
Embodiment 1
Using 1# municipal sludge raw material 95%, 3# steel mill mud raw material 5%, oxidant is O2,
In backward mud to be ground add complexing agent (lignosulfonates and the mixture of humate,
Adding proportion is 1:0.5, and addition is 0.5wt ‰) so that it is concentration reaches 7%, controls reaction
System temperature is 580 DEG C, and reaction pressure is 22MPa, and the mixing of municipal sludge and steel mill's mud is dirty
The mud time of staying in the first high-pressure gas-liquid separator is 15min, the first high-pressure gas-liquid separator
The outlets products of upper end obtains CO, N after air relief valve reduces pressure2、CH4Etc. mixed gas, wherein
Containing a small amount of CO2Gas, it is high that the lower end outlets products of the first high-pressure gas-liquid separator enters second
Calming the anger liquid/gas separator, upper end product obtains highly purified CO after air relief valve reduces pressure2Gas, under
End product enters depressurizing system, and decompression afterproduct is the pulp water rich in metal-oxide, in pulp water
COD COD of liquid is 20mg/L, reaches national grade one discharge standard, can reuse
As raw water, isolated solid slag is used for reclaiming flocculant and metal-oxide.
Embodiment 2-8
The detailed process of embodiment 2-8 sees embodiment 1, and the relevant parameter in each embodiment sees
Table 4-5.
Table 4 embodiment 1-4
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Municipal sludge raw material | 1# mud 95% | 1# mud 85% | 2# mud 90% | 2# mud 70% |
| Steel mill's mud raw material | 3# mud 5% | 4# mud 15% | 4# mud 10% | 5# mud 30% |
| Oxidant | O2 | Air | O2 | Air |
| Concentration wt% | 7 | 10 | 15 | 20 |
| Reaction temperature DEG C | 580 | 420 | 450 | 450 |
| Reaction pressure MPa | 22 | 23 | 25 | 24 |
| Time of staying min | 15 | 20 | 30 | 50 |
| b3COD*mg/L | 20 | 16 | 5 | 5 |
Note: COD* is COD；Municipal sludge and steel mill's mud distribute according to percent, and altogether 100%.
Table 5 embodiment 5-8
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Municipal sludge raw material | 1# mud 90% | 1# mud 85% | 2# mud 80% | 2# mud 75% |
| Steel mill's mud raw material | 3# mud 10% | 4# mud 15% | 4# mud 20% | 6# mud 25% |
| Oxidant | O2 | H2O2 | Air | O2 |
| Concentration wt% | 8 | 10 | 15 | 20 |
| Reaction temperature DEG C | 390 | 420 | 480 | 900 |
| Reaction pressure MPa | 23 | 23 | 26 | 26 |
| Time of staying min | 20 | 20 | 30 | 50 |
| b3COD*mg/L | 15 | 20 | 5 | 10 |
Note: COD* is COD；Municipal sludge and steel mill's mud distribute according to percent, and altogether 100%.
From the foregoing, it will be observed that the method for sludge treatment that the embodiment of the present invention is provided can make mixing sludge exist
Supercritical water reacts rapidly with oxidant and is thoroughly decomposed, generate CO2Gas and richness
The pulp water of containing metal oxide.The method not only can be to CO2Realize recycling, also can make
N in organic matter, S, P element have obtained effectively converting, it is achieved that harmless treatment.With
Time, owing to containing transition metal in large quantities in steel mill's mud, it is made at supercritical water oxidation
With the lower effect being played catalysis oxidation, also achieve the enrichment of transition metal, especially have
It is beneficial to the later stage harmless treatment containing heavy metal element mud, reduces the negative shadow in terms of environment
Ring.
Obviously, above-described embodiment is only for clearly demonstrating example, and not to reality
Execute the restriction of mode.For those of ordinary skill in the field, at the base of described above
Can also make other changes in different forms on plinth.Here without also cannot be to all
Embodiment give exhaustive.And the obvious change thus extended out or variation are still located
Protection domain in the invention.
Claims (11)
1. a method for sludge treatment, it is characterised in that including:
Municipal sludge and steel mill's mud are mixed, obtains mixing sludge；
After described mixing sludge is ground, sieves, it is carried out heat exchange and sends into reactor
In；
In described reactor, described mixing sludge in the supercritical state with oxidant generation oxygen
Change reaction, reaction of formation product；
Described reaction product carries out high-pressure gas-liquid separation after cooling, obtains power tail gas, CO2
Gas and the pulp water rich in metal-oxide.
Method for sludge treatment the most according to claim 1, it is characterised in that described steel mill
Mud accounts for the 5～30% of the mass percent of described mixing sludge.
Method for sludge treatment the most according to claim 1 and 2, it is characterised in that described
Steel mill's mud includes the transition gold selected from Fe, Mn, Ni, Cr, Mo, V, Ti, Zn, Cu
Belonging to, to account for the mass percentage of described steel mill mud, Fe is 5～50%, and Mn is 0.1～10%,
Ni is 0.1～20%, and Cr is 0.1～15%, and Mo is 0.05～5%, and V is 0.01～3%, and Ti is
0.01～2%, Zn are 0.02～5%, and Cu is 0.1～10%.
Method for sludge treatment the most according to claim 1, it is characterised in that described reaction
Product carries out high-pressure gas-liquid separation after cooling, obtains power tail gas, CO2Gas and rich in gold
The pulp water belonging to oxide includes:
In the first high-pressure gas-liquid separator, described reaction product is carried out one-level high-pressure gas-liquid to divide
From, to generate power tail gas and intermediate reaction product；
In the second high-pressure gas-liquid separator, described intermediate reaction product is carried out two grades of high pressure gas
Liquid separates, to generate CO2Gas and the pulp water rich in metal-oxide.
Method for sludge treatment the most according to claim 1, it is characterised in that described oxidation
Agent is selected from any one in air, oxygen and hydrogen peroxide.
Method for sludge treatment the most according to claim 1, it is characterised in that described oxidation
The operation pressure of reaction is 22～30MPa, and temperature is 380～900 DEG C.
Method for sludge treatment the most according to claim 6, it is characterised in that described oxidation
The operation pressure of reaction is 22～26MPa, and temperature is 420～650 DEG C.
Method for sludge treatment the most according to claim 4, it is characterised in that described reaction
The product time of staying in described first high-pressure gas-liquid separator is 5～60min.
Method for sludge treatment the most according to claim 8, it is characterised in that described reaction
The product time of staying in described first high-pressure gas-liquid separator is 15～40min.
Method for sludge treatment the most according to claim 4, it is characterised in that described
The inlet temperature of one high-pressure gas-liquid separator is below 31 DEG C, and outlet pressure is at more than 7.38MPa.
11. method for sludge treatment according to claim 1, it is characterised in that to institute
State mixing sludge be ground and sieve front or rear, in described mixing sludge, add complexing agent,
To improve the concentration of described mixing sludge.
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| CN105300139A (en) * | 2015-06-10 | 2016-02-03 | 大连东方亿鹏设备制造有限公司 | Hypercritical oxidation sludge heat exchanger |
| CN105036501B (en) * | 2015-08-05 | 2017-05-03 | 新奥科技发展有限公司 | Sludge degradation treatment method |
| CN105174675A (en) * | 2015-08-28 | 2015-12-23 | 中国海洋石油总公司 | Treatment method for coal-gasification wastewater biochemical sludge |
| CN105057318A (en) * | 2015-09-07 | 2015-11-18 | 新奥科技发展有限公司 | Carbonic waste degradation treatment method and carbonic waste degradation treatment equipment |
| CN106608700A (en) * | 2015-10-22 | 2017-05-03 | 王冰 | Supercritical system and method used for increasing low COD waste water calorific value with bacteria-alga |
| CN106734055A (en) * | 2016-11-22 | 2017-05-31 | 中国科学院重庆绿色智能技术研究院 | A kind of on-site treatment method of oil gas field well site oil-based drill cuttings |
| CN107601803A (en) * | 2017-09-18 | 2018-01-19 | 中海油能源发展股份有限公司 | A kind of material hardening and tempering method of supercritical water oxidation processing sludge |
| CN109020131A (en) * | 2018-09-10 | 2018-12-18 | 遵义师范学院 | A kind of waste plastic and municipal sludge co-oxidation processing unit and method |
| CN110699543B (en) * | 2019-11-22 | 2020-12-25 | 中南大学 | Method for preparing iron ore sintered pellet binder by using steel oily sludge, binder and application |
| CN115555387A (en) * | 2022-09-12 | 2023-01-03 | 昆明理工大学 | Method for degrading plastics in waste water and sludge |
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